Derivatives of amino-benzo-p-dioxans



Patented Apr. 22, 1947 OXAN Robert C. Conn and Frederic H. Adams, Bound Brook, and John P. Goulding, Neshanic Station, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application December 10, 1943, Serial No. 513,734

Claims.

This invention relates to a new series of chemical compounds comprising N-substituted derivatives of monoaminobenzo-p-dioxans.

These amino-dioxans may be illustrated, for

example, by G-amino-1,4-benzodioxan, which for I the purposes of the present invention may be represented by the following formula:

or by '7--amino-benzo-p-dioxeno-p-dioxan having the following analogous structure:

radical represented and numbered for purposes of the present invention as HzN 3 ll in which X may represent a hydrogen, halogen, nitro, carboxy or sulfonic radical, the acyl radical of a carboxylic acid, or a sulfonamide group.

The instant application relates to the new organic bases per se. Azo dyes, particularly icecolors, having novel color shades and unusual light fastness may be derived therefrom. These new dyestuffs comprise the subject matter of our copending application for United States Letters Patent, Serial No. 513,777, filed of even date.

Very few aromatic amino compounds have been known which produce on diazotization and coupling with an ice-color coupling component strong blue to violet shades. It is one of the principal objects of the present invention to produce a new series of bases and ice-colors derived therefrom which will have these desirable shades. It is a further object of the invention to produce a series of bases suitable, for the production of other azo dyes and to develop such dyes therefrom.

In general, the principal objects of the present invention are accomplished by condensing the amino-benzo-para-dioxan with a para-nitrohalogenobenzene and subsequently reducing the nitro group to an amino group; The resulting 2 new compounds, after diazotization and coupling, yield. dyestuffs which have desirable properties.

Either para-nitrohalogenobenzene or a paranitrohalogenobenzene containing a negative substituent ortho to the halogen radical may be used as a starting material. ents may include radicals such as halogen, nitro, carbon, or sulfonicradicals, the acyl radical'of a 'carboxylic acid or a sulfonamide group. In any case, after condensation and reduction the product constitutes an N-para-aminophenyl-substituted aminobenzodioxan. Therefore, as used in the instant application, the expression a paraaminophenyl radical includes not only the-paraaminophenyl radical, but also those 2-substituted-4-aminophenyl groups in which the negative substituents are present.

Similarly, for the purposes of the present invention, the expression a sulfonamide radicais used to designate not only the H group, but also N-substituted-sulfonamides. In the latter case, the sulfonamide group may be one in which either or both of the hydrogens are substituted by an alkyl or aryl radical or one in which the substituents form with the nitrogen a heterocyclic ring such as a sulfonpiperidide, sulfonmorpholide or the like.

Those para-nitrohalogenobenzenes containing negative substituents, ortho to the halogen radical, are particularly useful. When such materials are used, condensation proceeds smoothly in aqueous media. The invention, however, is not necessarily so limited. Condensation maybe carried out in any solvent compatible with the solubility and reactivity of the particular nitrohalogenobenzene employed. In some cases, an anhydrous solvent such as nitrobenzene or the like is required. In some cases, also,the use of a cuprif-i erous catalyst may be of advantage. Generally, too, it is well to provide an acid binder such as a metal oxide, carbonate or the like.

Reduction of the nitro to an amino group may be carried out either by alkaline or by acidic reducing agents. The pH will determine whether free bases or salts will be produced. It will be apparent that two different types of salts are'possible. There may be acid salts of the base. On the other hand, when an acidic substituent such as a carboxylic or sulfonic group is present on the p-aminophenyl radical, the acidic constituent may be neutralized to form a salt. Both types of These negative substitusalts as well as the free bases are useful. Each may be converted to the other by appropriate treatment. Reference to the new bases in the instant specification and claims is therefore intended to include not only the bases themselves but also both types of salts thereof.

Diazotization of some bases of the present in- 4 tetrahydro-Z-hydroxy-3-naphthoic acid, of 2- hydroxy-3-anthroic acid, of methyl and dimethyl salicyclic acids, of hydroxy-benzoacridone carboxylic acids, of 3,7-dihydroxynaphthalene-2,6 dicarboxylic acid, of hydroxy-dibenzofuran carboxylic acids, of hydroxy benzothiophene car- "fbOXYllc acids, etc., and the arylides of acetovention in mineral acid solution by nitrous acid produces, according to the conditions imposed,..

two different products. In general, use of higher temperatures, greater concentration of the base in solution, higher mineral acid concentration and excess nitrous acid generally lead to formation of an N-nitroso derivative of the diazonium salts. Lower temperature, lower acid concentrations and controlled nitrous acid addition lead to formation of the diazonium chloride itself.

In general, the N-nitroso diazotization prodi ucts lead to the production of different, duller and less desirable shades when coupled. The simple diazotized products lead to the production of the more valuable and faster shades. Conversion of the N-nitroso colors to the more desirable shades is accomplished through hydrolysis of the former. This may be accomplished by heating the N-nitroso colors in dilute solutions of some alkaline material such as soda ash or the like. Reducing agents such as sodium sulfide, sodium bisulfite or their equivalents may be included in thev saponification bath to destroy nitric oxides as they are liberated.

'In their diazotized form. the bases may be coupled either with or without a substrate, to yield dyestuffs or pigments of great value because of their strength. variety of shade and fastness propert es. In particular, however, the bases of the present invention are important for the production of fast blue prints or dyeings upon cellulosic materials. These 'are produced in general, by impregnating the cellulosic material in alkaline baths with appropriate ice-color coupling components and then printing solutions of the diazotized bases which have been buifered and thickened upon such prepared cloth, or by pad dyeing the prepared cloth in buffered solutions of the diazotized bases or the diazo salts.

The bases of the present invent on may be also converted into diazo-sulfonates. If the basic portion of these diazo-sulfonates is'free from solubilizing groups, they may be blended with appropriate ice-color coupling components and oxidizing agents. Such blends may be incorporated into a printing paste, printed on vegetable fibers and the pigment developed by treatment with steam.

Substantially any of the ice-color coupling components are generally useful for production of insoluble, developed dyes, and enable the production of a variety of colors from yellow to blue. However, for the present purposes, the use of arylides of 2-hydroxy-3-naphthoic acid is preferable. These produce, when coupled with the diazotized bases of the present invention, the most desirable blue to violet shades.

However, the invention is not necessarily so limited. Among other ice-color coupling com ponents which-produce useful products may be listed by way of example such compounds as beta-naphthol, S-amino-Z-naphthol, S-acetylamino-Z-naphthol, benzoyl naphthols; pyrazolones and pyrazyl pyrazolones; hydroxy benzofluorenones; hydroxy derivatives of phenyl naphthylamines such as 7-hydroxy-1-naphthyl-mhydroxyphenylamine; particularly the various N-substituted amides such as arylides, of 5,6,7,8-

acetic acid, furoyl acetic acid, benzoyl acetic acid, terephthaloyl-bis-acetic acid and the like. The arylide grou in the coupling component may be asimple aromatic group such as the radical of aniline or of an aniline derivative or of a naphthylamine, or it may be the radical of a heterocyclic amine, such as, e. g., of an amine of the benzothiazole series or of a diamine of the diphenylene oxide or diphenylene sulfone series.

The bases of the present invention also may be used in the preparation of water-soluble dyestuffs suitable for dyeing vegetable or animal fibers. In this case, a great many of the customary phenolic or aminic coupling components may be used. The coupling component, however, must carry at least one sulfonic group in case the diazo component has none. Illustrative examples of such coupling components include salicyclic acid, resorcinol, m-phenylene diamine, the large number of naphthol-sulfonic acids such as e. g., R-acid, G-acid, the Cleves acids, J-acid, gamma-acid, J-acid urea and J-acid imide, H- acid and many others. Pyrazolones such as sulfonic derivatives of1-phenyl-3-methyl pyrazolone-5 also may be used;

If so desired, the new diazo components of the present invention also may be used for the production of disand poly-azo dyes in accordance with the customary procedures. Depending upon their structure, the dyes obtained from the new bases are direct dyes, acid wool dyes or chrome dyes. In each group, a great many of them have very Valuable dyeing and fastness properties.

The invention will be more fully illustrated in conjunction with the following examples which are meant to be illustrative only and not by way of limitation. All parts are by weight unless otherwise noted.

Example 1 133 parts of sodium 2-chloro-5-nitrobenzene sulfonate (61.8% purity) are condensed with 55.8 parts of 6-amino-1,4-benzodioxan in 400 parts of water in the presence of 50 parts of calcium carbonate by refluxing the mixture until reaction is substantially complete. Then 600 parts of water and 12 parts of ammonium chloride are introduced, and at reflux temperature parts of zinc dust are added in successive small portions. When the reaction mixture has become colorless, it is clarified and parts of hydrochloric acid (1.19) are added. The precipitated product is separated by filtration and is Washed with water on the filter. It has the formula HiN (llHa H OH:

N 0/ SOsH Example 2 terial remains. To the reaction mixture is added- HzN Example 3 0.8 part of the amine of Example 2 is dissolved in 4 parts of alcohol and run at 30 0., into a solution of 9 parts of zinc chloride and 0.3 party of sodium nitrite in parts of water. The precipitated product is filtered and the residue is washed with parts of water. The washings are-combined with the first filtrate and sodium chloride is added to complete precipitation. The

precipitated zinc chloride double salt is filtered and dried under vacuum.

Example 4 The zinc chloride double salt obtained in Example 3 is mixed with one-third of its weight of magnesium sulfate di-hydrate. 2 parts of this color mixture are dissolved in 25.5 parts of water containing 2 parts of 20% sodium acetate and 0.5 part of 50% acetic acid. 70 parts of a suitable carbohydrate thickener" are added. This color paste is printed from an engraved roll on cotton piece goods previously impregnated with the ortho-toluidide of 2-hydroxy-3-naphthoic acid from an alkaline solution, and the printed stripe is passed through a dilute soda ash solution at C., then soaped at the boil and finished by passing through a boiling 5% soda ash solution. A bright blue dyeing results with very good fastness properties.

Example 5 Example 6 1.15 parts of the zinc chloride double sal-tproduced as in Example 3 are dissolved in parts of water and 0.32 part of anhydrous sodium sulfite dissolved .in 2 /2 parts of water added, followed by 0.26'part of sodium carbonate. The reaction Example 77 1.6 parts or .N-(Z sulfo-Q-amino phenyl -6- amino-lA-benz'odioxane as obtainedin Example 1 are stirred in 25 parts of water and are dissolved by adding 0.2 ,part'sodium hydroxide. To the clear-solution are added 2.5 parts of hydrochloric acid 7 (1.19). The resultant slurry is cooled 'to 5 Q, and diazotized by adding 0.35 part of sodium nitrite dissolved in 5-parts of water. A solution of 1.5 parts of sym.-di-(5,5--hydroXy- '7,7'-sulfo- 2,2-naphthyl) urea dissolved in 60 parts of water containing 3.2 parts of soda ash is made, the temperature lowered to 5 C., and the diazo slurry is run in. An immediate deep blue color results, coupling being complete in about 15 minutes. At 70 C., the dyestuff is salted out by adding 20.0 parts of sodium chloride. After stirring for :15 minutes, the precipitate is filtered oif,'washed on the filter with 10% salt solution and dried'at .C. The resultant product is a deep blueblack powder readily solublein water, yielding a bright blue solution, and has the following formula:

'..' S'0 Na NB-Oas NHCONH' some NH on.

N=N N=N on,

OH H 0 Example 8 0.5 part of the dyestuif as prepared in Example '7 is dissolved in 500 parts of water. One-tenth of this solution is diluted with 150 parts of water and 4.0 parts of sodium'chloride are dissolved in the solution. 5.0 parts or" previously wet-out cotton piece goods are. entered into the dye bath. While agitating the cloth, the temperature of the dye bath is raised to and maintained. at the boil for one-half hour. At this time, the cloth is removed, rinsed fresh water, treated at C. in a 1% soap solution, rinsed again and dried. The cotton piece goods is levelly dyed a Example 9 One-tenth part of the standard dye solution as prepared in Example 8 is diluted with 150 parts of water, and then 2.0 parts of sodium sulfate and 2.0 parts of 5% sulfuric acid solution are added. 5.0 parts of well boiled-out wool flannel are. entered in this dye bath and while agitating efficiently the temperature is raised to theboil. After boiling for three-quarters of an hour, the cloth is removed, rinsed with fresh water, heated at C. in a 1% soap solution, rinsed in fresh water and dried. The wool flannel is dyed levelly a brilliant corinth.

Example 10 A diazo slurry is prepared as described in Example 7. This is stirred into a cold solution of 0.98 part of acetoacetanilide in 50 parts of water containing 0.23part of sodium hydroxideand 2.6 parts of soda ash. A tan precipitate forms immediately. When'coupling iscomplete, the temperature is raised to 40 C. and 15.0 parts of sodium chloride added. The brown precipitate is filtered oif and is dried at 45 C. A brown powder results which dissolves readily in water, yielding a yellow solution, and has the following for- SO aNz Example 11 0.2 part of the dyestufi prepared in Example 10 is dissolved in 200 parts of Water to which is added 2.0 parts of sodium sulfate and 2.0 parts of 5% sulfuric acid. 5.0 parts of wool flannel previously well boiled out are entered and the solution is gently boiled. for one-half hour. The cloth is removed, rinsed in fresh water, heated at 65 C. in 1% soap solution, rinsed in fresh water and dried. A strong, golden yellow dyeing results.

Example 12 38.8 parts of benzo-p-dioxeno-p-dioxan are dissolved in 420 parts of glacial acetic acid containing 30 parts of sulfuric acid (1.84) and are nitrated at 30 C. by the addition of 12.6 parts of a mixed acid (28% nitric acid; 56% sulfuric acid). The temperature is maintained at 30-50 during the addition of the mixed acid and then is held at 5060 C. for about 30 minutes. After drowning in ice and water and stirring until solidification is complete, 'l-nitro-benzo-p-dioxeno-pdioxan is separated by filtration. On recrystallization from alcohol, the product melts at 130- 131 C. It has the formula Example 13 33 parts of the nitrobenzo-p-dioxeno-p-dioxan produced in Example 12 are dissolved in 800 parts of water containing 6.5 parts of glacial acetic acid, 70 parts of iron filings added and the mixture stirred at 60 C. for about seven hours. 260 parts of benzene are added at the boiling point and the reaction mixture is cooled to room temperature. After filtration and separation of the benzene layer, the aqueous layer and residue are again extracted with 180 parts of hot benzene. The benzene extracts are dried. Addition of dry hydrogen chloride separates the hydrochloride which is filtered ofl", dissolved in water, the water solution clarified and the free amine precipitated by neutralizing the solution with soda ash. Crystallized from alcohol, the 'lamino-benzo-p-dioxeno-p-dioxan melts at 95- 96 C. It has the formula HzN Example 14 parts of 7-amino-benzo-p-dioxeno-p-dioxan are condensed with 7.7 parts of the sodium salt of 2-chloro-5-nitrobenzene sulfonic acid (89%) in 80 parts of water containing 2 parts of alcohol and 4 parts of calcium carbonate at the reflux for 48 hours. The reaction mixture is filtered while hot, and parts of ammonium chloride in 150 parts of water are added to the filtrate. The resultant mixture is brought to the boil 7 parts of zinc dust are strewn in portionwise. When the reaction mixture has become decolorized, it is filtered While hot, the filtrate acidified with acetic acid and the resultant white precipitate separated by filtration. The product, N-(2'-sulfo-4-amino henyl) -'l-aminobenzo -pdioxeno p dioxan'e has the formula 0 H 0 c \CH1 Example 16 The hydrochloride of Example 15 is diazotized in dilute hydrochloric acid solution at room temperature by the addition of sodium nitrite to a I permanent test against starch iodide paste. The

diazo solution so prepared is bufiered to a negative acid test against Congo red test paper by addition of sodium acetate solution and then sodium carbonate is added until the solution is neutral to litmus. Cotton cloth previously impregnated in an alkaline bath of the anilide of 2- hydroxy-3-naphthoic acid is pad dyed in the buffered diazo bath until color development is complete. The dyed cloth is treated in a dilute'soda ash solution at 40 C., boiled in a 5% soda ash solution and finished by soaping at elevated temperature, washingand drying. The cloth is dyed a strong blue.

We claim:

1. Chemical compounds selected from the group consisting of bases represented by the formula XNHY and the salts thereof in which X represents a mono nuclear p-amino aryl radical of the benzene series and NI-I--Y represents the residue of a heterocyclic compound selected from the group consisting of 6-aminobenzo-para-dioxan and l-amino-benzo-para-dioxeno-para-dioxan.

2. A chemical compound according to claim 1 in which X represents a mononuclear 4-amino- 2'-sulfo-phenyl radical.

3. Chemical compounds according to claim 1 in which X is The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Lubs et al Sept. 2, 1941 Number 

